EP2035350B1 - Éléments céramiques réfractaires d'oxyde métallique revêtus d'un métal du groupe platine ou d'un alliage d'un métal du groupe platine - Google Patents

Éléments céramiques réfractaires d'oxyde métallique revêtus d'un métal du groupe platine ou d'un alliage d'un métal du groupe platine Download PDF

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Publication number
EP2035350B1
EP2035350B1 EP07789014A EP07789014A EP2035350B1 EP 2035350 B1 EP2035350 B1 EP 2035350B1 EP 07789014 A EP07789014 A EP 07789014A EP 07789014 A EP07789014 A EP 07789014A EP 2035350 B1 EP2035350 B1 EP 2035350B1
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EP
European Patent Office
Prior art keywords
ceramic
metal
refractory
coating
slots
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EP07789014A
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German (de)
English (en)
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EP2035350A1 (fr
Inventor
Duncan Roy Coupland
Roger Charles Wilkinson
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Johnson Matthey PLC
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Johnson Matthey PLC
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
    • C04B41/5122—Pd or Pt
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/42—Details of construction of furnace walls, e.g. to prevent corrosion; Use of materials for furnace walls
    • C03B5/43—Use of materials for furnace walls, e.g. fire-bricks
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/85—Coating or impregnation with inorganic materials
    • C04B41/88—Metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • Y10T428/24612—Composite web or sheet

Definitions

  • the present invention concerns improvements in coated materials, and more especially concerns platinum group metal-coated ceramics.
  • Slip-cast and sintered ceramic refractories are used extensively as parts for the handling of aggressive materials such as molten glass.
  • Such sintered ceramic refractories are generally manufactured by forming a dense slurry of the refractory oxide, optionally in the presence of inorganic binding agents, casting the slurry in a mould and sintering the resulting cast item.
  • Such refractories are considered to be of low density, and generally exhibit up to 15-20% of interconnecting porosity.
  • Chemically, such refractories are mixtures of two or more of silica, alumina and zirconia, although other oxide components such as magnesia may be present, plus additives and impurities that may promote sintering etc.
  • fusion-cast refractories the chemical constituents are generally fused by electric arc melting using graphite electrodes, and cast into moulds or flowed onto enclosed surfaces.
  • the fusion-cast refractories find widespread use as furnace lining blocks and channel blocks and in furnace and reaction vessel linings (sometimes called "glass-lined vessels") and generally exhibit improved resistance to corrosion or erosion compared to low density refractories. The same is also true for the less commonly used pressed, engineering refractories mentioned above.
  • fusion-cast refractories and the pressed engineering refractories exhibit high performance in use, under extreme conditions they are still prone to attack and ultimate destruction.
  • high performance refractories are subject to attack at or below the line of molten glass.
  • the lifetime of such components is determined by temperature, glass-type and the amount of glass processed. Damage to these refractories, because of their use in strategic locations, can lead to the need for partial or even complete shut-down of the furnace and loss of production.
  • the present invention is believed to be applicable not just to fusion-cast and engineering ceramics for the glass industry, but to supported or unsupported ceramics and glasses which exhibit the same characteristics of at least a dense, low-porosity surface to which sprayed metals or similarly deposited metal films, show poor adhesion. All such materials are to be considered as metallic-oxide ceramic refractories within the scope of the present invention.
  • the present invention provides a refractory metallic-oxide ceramic part suitable for use in the processing of molten glass, said part possessing at least one surface area having a surface drilled to develop an array of slots or closed-end holes, and in which at least a portion of such treated surface carries a platinum group metal or platinum group metal alloy coating pegged thereto by the mechanical interaction between metal pegs formed as part of said coating and positioned within said slots or holes and the ceramic walls and bases of said slots or holes.
  • a suitable industrial laser can have substantially the same effect, is operational in a normal air atmosphere, and by using a fibre-optic delivery system attached to a multi- axis positioning system, the laser profiling can be achieved on both planar and non-planar surfaces.
  • a pattern of cut blind holes or indentations or slots can be achieved on a macroscopic scale, which is effective to give a keyed surface to which flame-sprayed metal adheres surprisingly well. It is not necessary for any of the blind holes, indentation or slots to have a re-entrant shape. It is not believed that the profile pattern is significant in achieving the remarkable results of the present invention, and it is thought that almost any regular, irregular or even random profile is effective.
  • the holes have a depth to diameter ratio of greater than one, preferably from 3 to 6, and slots have a width to diameter ration of greater than one.
  • Holes desirably have a diameter at the surface of the ceramic of 200 to 500 microns.
  • Slots desirably have a length to depth ratio of less than three; slots preferably have a width of 200 to 500 microns at the surface of the ceramic.
  • Slots need not be simple slots but may incorporate one or more changes in direction, and may intersect.
  • the spacing of holes or slots in an array may be determined according to the particular ceramic by routine experiment, but this is suitably less than 20 times the hole diameter.
  • a preferred linear spacing is approximately 1 mm.
  • the invention also provides a method of metal coating a metallic-oxide refractory ceramic part, comprising treating at least one surface area of said part using a high energy beam to remove a portion of surface area, to form a plurality of slots or closed-end holes which form an effective bonding surface, and subsequently depositing a coating of a platinum group metal or alloy thereof, onto the bonding surface to provide mechanical interaction between metal pegs formed as part of said coating and positioned within said slots or holes and the ceramic walls and bases of said slots or holes.
  • One surprising aspect of the experimental work has been the discovery that the flame or plasma sprayed metal penetrates deeply into the patterns cut by the energy beam and fills them without developing local through coating porosity.
  • the metals useful in the present invention are one or more of the platinum group metals, namely platinum, rhodium, palladium, ruthenium, iridium and osmium, and alloys with each other or with base metals.
  • the metal is platinum, an alloy of platinum, eg Pt5%Au, Pt10%Ir, Pt10%Rh, Pt5%Ru, or Pt with up to 1%Zr, or grain stabilised Pt or Pd.
  • platinum platinum
  • platinum platinum, an alloy of platinum, eg Pt5%Au, Pt10%Ir, Pt10%Rh, Pt5%Ru, or Pt with up to 1%Zr, or grain stabilised Pt or Pd.
  • the refractory part may be of any of the conventional fusion-cast refractory or pressure formed engineering refractory compositions, incorporating one or more of SiO 2 , Al 2 O 3 , ZrO 2 and MgO 2 , optionally including amounts of other refractory oxides such Cr 2 O 3 .
  • AZS alumina/zirconia/silica
  • Such high density engineering refractories are not defined by nomenclature but by suitability for the most arduous glass furnace applications.
  • Other similar refractory parts, such as fusion-cast chromias may be platinum-coated using the present invention.
  • zirconia In the casting process, zirconia has the highest melting point of the regular components of an AZS refractory, and tends to crystallise preferentially at the surface of the mould. This can result in the surface of the fusion-cast part not being representative of the bulk material, and can be less amenable to treatment. It may be desirable in such cases that the surface of the part is machined to expose bulk AZS material; in manufacturing certain parts this was done conventionally as part of the manufacturing process.
  • one or more intermediate metal oxide and/or metal layers may be applied, using conventional methods or methods known per se .
  • the platinum group metal may be deposited on the surface of the refractory part in a number of different ways.
  • a preferred method is by combustion flame spraying in a method analogous to that described in EP 0 559 330 .
  • Other methods include plasma flame spraying, and high velocity oxy-fuel combustion spraying. Further methods may be developed without departing from the scope of the present invention, and, for certain uses, sputtering or CVD may be appropriate.
  • the metal coating desirably has a thickness of 50 microns up to 2mm (the thickness is probably limited only by the economics). More desirably, the thickness is 50 to 500 microns, suitably about 200 microns.
  • platinum-coated fusion cast refractory and high density engineered refractory ceramic parts according to the invention are corrosion resistant at temperatures of up to 1600-1650° C. This can increase the processing options and materials available to furnace users.
  • the platinum group metal film may be connected to a source of electricity in a manner that permits resistance heating of the film. This can permit good temperature control of furnace contents and may reduce viscosity of furnace contents such as molten glass, in appropriate parts of the furnace.
  • Patterns 1 to 11 were prepared using the EB gun inside a vacuum chamber on a single block of fusion cast ceramic ER1711. The specific conditions of the processing were recorded and defined, but since these are specific to the particular EB gun and equipment, these conditions are not defined here. In practice the conditions required to define any selected pattern would need to be defined for the specific EB unit.
  • Table I Patch Pattern 1 Short lines, basket weave 2 Short lines, basket weave 3 Short lines, basket weave 4 Lines unbroken? 5 Lines unbroken? 6 Short lines, basket weave 7 Faint lines 8 Square grid of holes 9 Square grid of holes 10 Rows of holes 11 Square grid of holes
  • the level of ceramic movement from the zones of highest beam energy was considered extreme for some pattern types, specifically the weave and slot patterns.
  • the decision was made to grit blast the as treated surfaces.
  • the images shown in Figure 1 are of the surfaces after the grit blasting.
  • the coatability was excellent with the pattern being less important than having disrupted the surface very significantly to create holes or slots.
  • the additional benefit of the strong bond between coating and "pattern" was a carry over to the untreated areas of ceramic between the treated patches, where is appears that the bonding generated by the treatment has reduced interfacial stresses sufficiently to allow these regions also to be satisfactorily bonded.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Paints Or Removers (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Insulated Conductors (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Claims (15)

  1. Pièce de céramique réfractaire d'oxyde métallique convenant pour une utilisation dans le traitement du verre fondu, ladite pièce possédant au moins une surface de contact ayant une surface perforée pour développer un réseau de fentes ou de trous fermés à une extrémité, et dans laquelle au moins une partie d'une telle surface traitée porte un métal du groupe du platine ou un revêtement d'alliage de métal du groupe du platine chevillé à celle-ci par l'interaction mécanique entre les chevilles métalliques formées comme partie dudit revêtement et placées au sein desdites fentes ou trous et les parois et bases de céramique desdites fentes ou trous.
  2. Pièce de céramique selon la revendication 1, dans laquelle la céramique réfractaire est un réfractaire coulé par fusion ou technique.
  3. Pièce de céramique selon la revendication 2, dans laquelle la céramique réfractaire est un réfractaire pressé selon un mode isostatique ou hydrostatique, et fritté.
  4. Pièce de céramique selon la revendication 1, 2 ou 3, dans laquelle la céramique est composée d'un ou plusieurs parmi la silice, l'alumine, le zircone et la magnésie, et est de préférence un réfractaire AZS.
  5. Pièce de céramique selon la revendication 1, dans laquelle la céramique réfractaire est une céramique réfractaire coulée en barbotine et frittée.
  6. Pièce de céramique selon la revendication 5, dans laquelle la surface traitée est une surface concave.
  7. Pièce de céramique selon l'une quelconque des revendications précédentes, dans laquelle le métal est le platine ou un alliage de platine.
  8. Pièce de céramique selon l'une quelconque des revendications précédentes, dans laquelle le film est d'une épaisseur d'environ 200 à 500 microns.
  9. Four incorporant une pièce de céramique recouverte de métal selon l'une quelconque des revendications précédentes.
  10. Four selon la revendication 9, dans lequel le film métallique est relié à une source d'électricité et fournit une résistance au chauffage lorsqu'il est en marche.
  11. Procédé de revêtement métallique d'une pièce d'oxyde métallique réfractaire, comprenant le traitement d'au moins une surface de contact de ladite pièce en utilisant un faisceau de haute énergie pour supprimer une partie de la surface de contact, afin de former une pluralité de fentes ou de trous fermés à une extrémité qui forment une surface de liaison efficace, et le dépôt par la suite d'un revêtement d'un métal du groupe du platine ou d'un alliage de celui-ci, sur la surface de liaison afin de fournir une interaction mécanique entre les chevilles métalliques formées comme partie dudit revêtement et placées au sein desdites fentes ou trous et les parois et bases de céramique desdites fentes ou trous.
  12. Procédé selon la revendication 11, dans lequel le faisceau de haute d'énergie est un faisceau d'électrons.
  13. Procédé selon la revendication 11, dans lequel le faisceau de haute énergie est un faisceau laser.
  14. Procédé selon l'une quelconque des revendications 11 à 13, dans lequel le métal est déposé par projection à la flamme en combustion.
  15. Procédé selon l'une quelconque des revendications 11 à 14, dans lequel l'épaisseur de métal déposé est d'environ 200 à 500 microns.
EP07789014A 2006-06-23 2007-06-22 Éléments céramiques réfractaires d'oxyde métallique revêtus d'un métal du groupe platine ou d'un alliage d'un métal du groupe platine Active EP2035350B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0612399.6A GB0612399D0 (en) 2006-06-23 2006-06-23 Improvements in coated materials
PCT/GB2007/002326 WO2007148104A1 (fr) 2006-06-23 2007-06-22 Éléments céramiques réfractaires d'oxyde métallique revêtus d'un métal du groupe platine ou d'un alliage d'un métal du groupe platine

Publications (2)

Publication Number Publication Date
EP2035350A1 EP2035350A1 (fr) 2009-03-18
EP2035350B1 true EP2035350B1 (fr) 2009-10-21

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EP07789014A Active EP2035350B1 (fr) 2006-06-23 2007-06-22 Éléments céramiques réfractaires d'oxyde métallique revêtus d'un métal du groupe platine ou d'un alliage d'un métal du groupe platine

Country Status (9)

Country Link
US (1) US20100015399A1 (fr)
EP (1) EP2035350B1 (fr)
JP (1) JP2009541201A (fr)
KR (1) KR20090023403A (fr)
CN (1) CN101573311A (fr)
AT (1) ATE446281T1 (fr)
DE (1) DE602007002912D1 (fr)
GB (1) GB0612399D0 (fr)
WO (1) WO2007148104A1 (fr)

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DE102010047896B4 (de) * 2010-10-11 2016-03-03 Heraeus Deutschland GmbH & Co. KG Reduktion der Abdampfrate aus Platin und Pt-Legierungen: Bauteil und Verfahren
JP5821948B2 (ja) * 2011-03-28 2015-11-24 旭硝子株式会社 溶融ガラス保持用耐火物、および、溶融ガラス保持用耐火物を用いたガラス製造装置、ならびに、該ガラス製造装置を用いたガラス製造方法
CN102499773B (zh) * 2011-11-07 2014-04-16 中国矿业大学 提高钛瓷结合强度的钛表面加工方法
WO2014144152A1 (fr) 2013-03-15 2014-09-18 Rolls-Royce Corporation Interface de revêtement améliorée
KR20150008739A (ko) * 2013-07-15 2015-01-23 주식회사 케이티 개인화된 비디오 기반의 화면을 제공하는 서버 및 방법, 그리고 디바이스
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US10412570B2 (en) * 2016-02-29 2019-09-10 Google Llc Broadcasting device status
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CN113051522B (zh) * 2021-03-31 2022-01-25 成都飞机工业（集团）有限责任公司 一种自动火焰铝喷涂电阻的标定方法

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GB0612399D0 (en) 2006-08-02
KR20090023403A (ko) 2009-03-04
CN101573311A (zh) 2009-11-04
ATE446281T1 (de) 2009-11-15
WO2007148104A1 (fr) 2007-12-27
EP2035350A1 (fr) 2009-03-18
JP2009541201A (ja) 2009-11-26
US20100015399A1 (en) 2010-01-21
DE602007002912D1 (de) 2009-12-03

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